TW202309258A - Detergent composition for hard articles - Google Patents

Abstract

The present invention is a detergent composition for hard articles, the detergent composition containing component (a), component (b), and component (c), wherein: (a)/(c), which is the mass ratio of the component (a) content and the component (c) content, is 0.40-5.0; and the composition optionally contains (d) one or more surfactants selected from betaine-type surfactants and amide-type non-ionic surfactants [referred to as component (d) hereinafter], the component (d) content being less than 10 mass% relative to the total amount of surfactant in the composition. Component (a): polyoxyalkylene alkyl or alkenyl amine having a C6-20 alkyl group or alkenyl group and moreover having an average number of added mol of oxyalkylene groups of 1-5. Component (b): one or more surfactants selected from non-ionic surfactants and anionic surfactants (however, excluding component (a) and amide-type non-ionic surfactants). Component (c): solvent.

Description

Cleaner composition for hard objects

The invention relates to a cleaning composition for hard articles and a cleaning method for hard articles.

Generally speaking, as a kitchen cleaner used around the kitchen such as stoves, ovens, walls or floors around the stove, ventilation fans, etc., or as a cleaner used in food processing equipment, the use of surfactants, solvents and alkalis, etc. Cleaning agent to remove all kinds of dirt such as dirt from food, dirt from ingredients used for cooking, etc.

In Japanese Patent Laid-Open No. 2020-97711, a liquid detergent composition is disclosed, which contains (a) an amine oxide-type surfactant having a hydrocarbon group with a carbon number of 7 to 18, and (b) HLB under specified conditions. (Hydrophile Lipophile Balance, hydrophilic/oil ratio) is a nonionic surfactant of 1 to 10, and (c) a compound represented by the specific general formula (c1) having an alkyl group with a carbon number of 1 to 5. In Japanese Patent Laid-Open No. 2020-90606, a detergent composition is disclosed, which includes (A) anionic surfactant, (B) nonionic surfactant, and (C) dihydroxyethylglycine and At least one of its salts, and at least one of (C) dihydroxyethylglycine and its salts is 0.1 to 50 parts by mass. In Japanese Patent Laid-Open No. 2019-210475, a liquid detergent composition for tableware and/or hard objects around the kitchen is disclosed, which contains (a) a nonionic surfactant with an HLB of 10.5 or less (but (b) Excluding), (b) glycosides with hydrocarbon groups with carbon numbers of 8 to 18 and glycoside groups with an average condensation degree of 0.5 to 3, and (c) organic solvents with a logPow of 0 to 1.5, among the total surfactants The content of (a) is not less than 30% by mass and not more than 95% by mass, the mass ratio of the content of (c) to the content of (a) (c)/(a) is not less than 2 and not more than 8, and the viscosity at 20°C is Below 20 mPa・s. In Japanese Patent Laid-Open No. 2020-15863, a liquid cleaner composition for hard surfaces is disclosed, which contains a surfactant, and contains (A) a nonionic surfactant, and optionally contains (B) an amphoteric interface Active agent As a surfactant, in the surfactant, the ratio of (A) is 60% by mass or more, (A1) the carbon number of the alkyl group is 10 to 18, and the carbon number of the alkanol group is 2 or 3 Alkyl mono- or dialkanolamine or its alkylene oxide adduct (the carbon number of the alkylene oxide is 2 or 3) as (A), in the total of (A) and (B), (A1) The ratio is not less than 0.5% by mass and not more than 20% by mass. In Japanese Patent Application Laid-Open No. 2020-200420, a liquid bactericidal detergent composition is disclosed, which contains (A) anionic surfactant, (B) long-chain alkyl di-short-chain alkyl hydroxyethyl ammonium salt, ( C) a nonionic surfactant compound having a specific structure, (D) at least one selected from nonionic surfactants and amphoteric surfactants other than (C), (E) a solvent, and (F) water.

Oil stains attached to the dirt of tableware or cooking utensils are modified by heat, light, oxygen in the air, etc., and become very difficult to remove dirt (modified oil stains). Therefore, cleaning agents for tableware or cooking utensils are required to have a higher cleaning power on oil stains.

In addition, when cleaning dirt adhering to tableware or cooking utensils, the cleaning agent may be made to adhere to the object by foaming the sponge or spray. The foam of the cleaning agent not only adheres to the dirt to improve the cleaning efficiency, but also has the effect of making the operator feel that the cleaning operation is in progress and continuous.

In one aspect, the present invention provides a cleaning composition for hard objects that is excellent in cleaning power against oily stains and excellent in the persistence of foam.

As mentioned above, oil stains among stains attached to tableware or cooking utensils are modified by heat, light, oxygen in the air, etc., and become very difficult to remove stains (modified oil stains). Also, cleaning agents for tableware or cooking utensils are required to be excellent in high cleaning power against modified oil stains.

In another aspect of the present invention, there is provided a cleaning composition for hard articles which is excellent in cleaning power against oily stains such as modified oily stains.

In one aspect, the present invention relates to a cleaning composition for hard articles [hereinafter, also referred to as cleaning composition (I) for hard articles], which contains the following (a) component, the following ( b) ingredients and the following (c) ingredients, and The mass ratio of the content of (a) component to the content of (c) component (a)/(c) is not less than 0.40 and not more than 5.0, Optionally contain (d) one or more surfactants selected from betaine-type surfactants and amide-type nonionic surfactants [hereinafter referred to as (d) component], and the content of (d) component is relative to the composition The total amount of the surfactant in it is less than 10% by mass. (a) Component: polyoxyalkylene alkyl or alkenylamine having an alkyl or alkenyl group with a carbon number of 6 to 20, and the average addition molar number of the oxyalkylene group is 1 to 5 Component (b): One or more surfactants selected from nonionic surfactants and anionic surfactants (however, component (a) and amide-type nonionic surfactants are excluded) (c) Ingredient: solvent

In addition, the present invention relates to a cleaning method for hard objects in which the hard object cleaning composition (I) of the present invention is in contact with a hard object with dirt [hereinafter also referred to as the method for cleaning hard objects (I) ].

In another aspect, the present invention relates to a cleaning composition for hard articles [hereinafter, also referred to as cleaning composition for hard articles (II)], which contains the following ( _ax ) component and the following (b _x ) component, and the hydrophilic-lipophilic index of the composition as a whole is not less than 9 and not more than 14.2. Component (a _x ): polyoxyalkylene alkyl or alkenylamine having an alkyl or alkenyl group with a carbon number of 8 to 18, and the average addition molar number of the oxyalkylene group being 1 to 5 ( b _x ) component: nonionic surfactant (however, (a _x ) component and amide type nonionic surfactant are excluded)

In addition, the present invention relates to a cleaning method of a hard object in which the hard object cleaning composition (II) of the present invention is brought into contact with a hard object with dirt on it [hereinafter also referred to as the hard object cleaning method (II) ].

According to one aspect of the present invention, there is provided a cleaning composition for hard objects which is excellent in cleaning power against oily stains and excellent in the persistence of foam.

According to another aspect of the present invention, there is provided a cleaning composition for hard articles which is excellent in cleaning power on oily stains such as modified oily stains.

＜Cleansing composition for hard objects (I)＞ The mechanism by which the effects of the present invention appear may not be fully elucidated, but the applicant considers the following. Among the modified oil stains, the modified oil stains attached to cooking utensils or cooking equipment, etc. are highly modified due to heat history, etc. In order to peel off the object during cleaning, it is considered advantageous to use a cleaner with relatively high hydrophobicity . However, this kind of cleaning agent generally has low foaming performance, and when cleaning oil stains with a relatively low degree of modification such as tableware, the low-modified oil stains show foam-breaking properties, so the foaming performance is insufficient. decrease in volume and efficiency. Also, if foaming is considered in order to preferentially clean tableware with relatively hydrophilic dirt and less modification, the cleanability of kitchen counters and stoves with more highly modified dirt will decrease. When component (a) and component (b) of the cleaning composition (I) for hard articles of the present invention are adsorbed to modified oil stains, etc., for example, through an alkyl group as a hydrophobic group, it is considered that component (a) Since the addition molar number of the oxyalkylene moiety as a hydrophilic group is small, it is adsorbed near the adsorption interface, or extends the adsorption in the horizontal direction relative to the adsorption interface at a position far away from the adsorption interface, and the (b) component is a hydrophilic group. A moiety, such as an oxyalkylene moiety, is adsorbed with relatively a degree of freedom in a vertical direction with respect to the adsorption interface. The component (c) rapidly promotes aggregation in the formation of molecular aggregates of the components (a) and (b), and coexists in the molecular aggregates of the components (a) and (b). Also, the component (c) changes the hydrophobicity of the dirt surface by pre-adsorbing on the dirt surface or existing near the dirt surface. From such behavior, it is speculated that the component (c) has the effect of imparting a lipophilic/hydrophilic balance that is easily adsorbed on the surface of modified oil stains and the like. The (a) component and (b) component with such adsorption characteristics can not meet the performance requirements for highly modified oil and low modified oil even if the hydrophilic and hydrophobic properties are adjusted with a single structure. When component (a) and component (b) coexist, it is predicted that the density of the hydrophilic group near the hydrophobic group will be higher, and the hydrophilic region will have a wide molecular aggregate away from the dirt interface. In the case of such surfactants forming molecular aggregates, it is considered that even if the molecular aggregates are easily adsorbed on highly modified oil stains with relatively high hydrophobicity and are easily peeled off from highly modified oil stains with relatively high hydrophobicity , but due to the strong structure of the hydrophilic group, even if the relatively hydrophilic low-modified oil component is dispersed and stabilized, it is not easy to produce the foam-breaking effect from the oil. Therefore, it is considered that the detergency against highly modified oil stains can be maintained, and even for low modified oil stains, it is not easy to break the foam and can maintain the cleaning foam, so it can take into account the maintenance of cleaning power. On the other hand, it is considered that betaine-type surfactants or amide-type surfactants will affect the lipophilic/hydrophilic balance of component (c), and reduce the adsorption of component (c) to modified oil stains. Moreover, it is considered that component (d) easily interacts with component (a) due to the betaine group or amide group, and is also considered to be a factor that hinders the effect of component (a). Therefore, care must be taken when the component (d) is contained. Furthermore, the effect of the present invention is not limited to the mechanism of action shown here.

The component (a) is a polyoxyalkylene alkyl or alkenyl amine having an alkyl or alkenyl group having 6 to 20 carbon atoms and an average added mole number of the oxyalkylene group being 1 to 5.

From the viewpoint of maintaining a certain cleansing power and increasing the amount of cleansing through the continuation of the foam (hereinafter referred to as "the persistence of the cleansing foam"), the carbon of the alkyl or alkenyl group contained in the component (a) The number is 6 or more, preferably 8 or more, more preferably 10 or more, and is 20 or less, preferably 18 or less. (a) The group which the component has is preferably an alkyl group. The oxyalkylene group is preferably an oxyalkylene group having 2 carbon atoms and/or an oxyalkylene group having 3 carbon atoms, that is, an oxyethylene group and/or an oxypropylene group, more preferably an oxyethylene group. The component (a) preferably contains an oxyethylene group as the oxyalkylene group. From the viewpoint of detergency, the average added mole number of the oxyalkylene group of the component (a) is 1 to 5, preferably 1.5 or more, more preferably 2 or more, and more preferably 4.5 or less.

As the component (a), for example, an alkyl group or alkenyl group having 6 or more carbon atoms, 8 or more carbon atoms, and 20 or less, or 18 or less carbon atoms, and the average added mole number of the oxyalkylene group is 1 or more Alkylene oxide adducts of monoamines with a value of 5 or less.

As (a) component, the compound represented by following general formula (a1), for example is mentioned.

[chemical 1]

[In the formula, R is an alkyl group or alkenyl group with a carbon number of 6 to 20, EO is an ethoxyl group, m and n are the average addition moles, and are independently numbers of 0 to 5, m and n The total is more than 1 and less than 5]

In the formula (a1), the carbon number of R may be 6 or more, further 8 or more, further 10 or more, and 20 or less, further 18 or less. R is preferably an alkyl group. The total of m and n is preferably at least 1.5, more preferably at least 2, and more preferably at most 4.5.

The HLB of the component (a) is, for example, preferably at least 9, more preferably at least 9.5, and preferably at most 14.2, more preferably at most 13.0, from the viewpoint of ease of acquisition and durability of cleansing foam. (a) The HLB of the component was proposed by Griffin. Furthermore, in the present invention, the value of HLB corresponding to the actual measured value by the Griffin method in the following examples can be regarded as the HLB by the Griffin method. The same applies to HLB of other surfactants such as (b) component.

From the viewpoint of the persistence of the cleansing foam, the cleaning composition (I) for hard articles of the present invention may contain, for example, preferably at least 0.01% by mass, more preferably at least 0.05% by mass, and still more preferably at least 0.1% by mass The above, and preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less of the component (a).

From the viewpoint of the persistence of the cleansing foam, the cleaning composition (I) for hard articles of the present invention may contain, for example, preferably 0.1% by mass or more, more preferably 1% by mass or more, more preferably 10% by mass or more, more preferably 60% by mass or less, more preferably 55% by mass or less, further preferably 50% by mass or less of the component (a). The total amount of surfactant is the total amount of (a) component, (b) component, and any other surfactants contained in the cleaning composition (I) for hard articles, such as any content of (d) component. quantity. The cleaning composition (I) for hard articles of the present invention is a composition containing a surfactant, and may also be a composition containing (a) component, (b) component, and optionally containing (d) component as a surfactant .

Component (b) is one or more surfactants selected from (b1) nonionic surfactant [hereinafter referred to as (b1) component] and (b2) anionic surfactant [hereinafter referred to as (b2) component] (However, component (a) and amide-type nonionic surfactants are excluded).

Component (b1) may, for example, be selected from (b11) polyoxyalkylene alkyl ether [hereinafter referred to as (b11) component], (b12) alkyl (poly) glycoside [hereinafter referred to as (b12) Component], (b13) polyoxyalkylene fatty acid ester [hereinafter referred to as (b13) component], (b14) polyglycerin fatty acid ester [hereinafter referred to as (b14) component], and (b15) (poly ) one or more nonionic surfactants of oxyalkylene sorbitan fatty acid ester [hereinafter referred to as (b15) component]. When the cleaning composition (I) for hard objects of the present invention contains component (b1), the composition preferably contains one or more nonionic surfactants selected from component (b11) and component (b12) As (b1) component, it is more preferable to contain at least one type of nonionic surfactant selected from (b12) component as (b1) component.

The oxyalkylene group of the component (b11) is preferably an oxyalkylene group with 2 carbons and/or an oxyalkylene group with 3 carbons, that is, an oxyethylene group and/or an oxypropylene group, more preferably an oxyalkylene group. ethyl. From the viewpoint of the sustainability of the cleansing foam, the average added mole number of the oxyalkylene group of the component (b11) is preferably 0 or more, more preferably 1 or more, and is preferably 25 or less, more preferably 23 the following. The component (b11) preferably contains an oxyethylene group as the oxyalkylene group. The carbon number of the alkyl group of the component (b11) is preferably 3 or more, more preferably 4 or more, and preferably 30 or less, more preferably 24 or less, from the viewpoint of the sustainability of the cleansing foam. The alkyl group of the component (b11) may be a straight chain or a branched chain, but is preferably a straight chain from the viewpoint of the sustainability of the cleansing foam. The alkyl group of the component (b11) may be saturated or unsaturated, but is preferably saturated from the viewpoint of the sustainability of cleansing foam.

The carbon number of the alkyl group of the component (b12) is preferably 3 or more, more preferably 4 or more, and preferably 30 or less, and still more preferably 24 or less, from the viewpoint of the sustainability of the cleansing foam. Also, the average condensation degree of sugars such as glucose in the component (b12) is preferably 1 or more, more preferably 10 or less, and further preferably 5 or less from the viewpoint of the persistence of cleansing foam. The component (b12) is preferably an alkyl (poly)glycoside whose structural sugar is glucose. Component (b12) is preferably an alkyl (poly)glucoside having an alkyl group having a carbon number of 3 or more, further 4 or more, and 30 or less, further 24 or less, and the average degree of condensation of glucose is 1 or more and 10 or less, and further 5 or less.

The HLB of the component (b1) is, for example, preferably at least 9, more preferably at least 9.5, and preferably at most 17.4, more preferably at most 16.9, from the viewpoint of easy availability and cleanability. The HLB of the component (b1) is obtained by the Griffin method. As mentioned above, the hydrophilic-lipophilic index measured by a predetermined method can be regarded as the HLB of the component (b) obtained by the Griffin method.

Examples of the component (b2) include: fatty acid salt (preferably having 8 to 24 carbon atoms), alkyl (preferably having 8 to 24 carbon atoms) sulfonate, alkyl (preferably having 8 to 24 carbon atoms) More than 18 but less) benzene sulfonate, alkyl (preferably carbon number 8 to 24) sulfate ester salt, alkyl (preferably carbon number 2 to 24) phosphate ester salt, polyoxyalkylene (more Preferably polyoxyethylene) alkyl (preferably 8 to 18 carbons) sulfate ester salt, polyoxyethylene (preferably polyoxyethylene) alkyl (preferably 8 or more carbons) 18 or less) carboxylate or alkyl (preferably 6 to 18 carbon number) sulfosuccinate, etc. Salts may, for example, be alkali metal salts such as sodium salts or potassium salts.

From the viewpoint of the persistence of the cleansing foam, the cleaning composition (I) for hard articles of the present invention may contain, for example, preferably at least 0.1% by mass, more preferably at least 0.5% by mass, and still more preferably at least 1% by mass The above, and preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less of the component (b).

From the viewpoint of the persistence of the cleansing foam, the cleaning composition (I) for hard objects of the present invention may contain, for example, preferably 10% by mass or more, more preferably 15% by mass or more, more preferably 20% by mass or more, more preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less of the component (b).

Regarding the cleansing agent composition (I) for hard articles of the present invention, from the viewpoint of the persistence of the cleansing foam, the mass ratio of the content of the component (a) to the content of the component (b) is (a)/(b) For example, it is preferably at least 0.01, more preferably at least 0.05, still more preferably at least 0.1, even more preferably at least 0.15, even more preferably at least 0.18, and is more preferably at most 3, more preferably at most 2, and still more preferably 1 or less, still more preferably 0.5 or less, still more preferably 0.3 or less, still more preferably 0.23 or less.

(c) The component is a solvent. Component (c) may, for example, be selected from (c1) glycerin ether [hereinafter referred to as component (c1)], (c2) glycol ether [hereinafter referred to as component (c2)], and (c3) polypropylene glycol [Hereafter, referred to as (c1) component] at least one solvent.

The glycerin ether as the component (c1) is preferably an alkyl glyceryl ether having an alkyl group having 5 or more carbon atoms, further 6 or more carbon atoms, and 10 or less, further 9 or less alkyl groups. The above-mentioned alkyl glyceryl ether is preferably a monoalkyl glyceryl ether. As (c1) component, 2-ethylhexyl glyceryl ether is preferable.

The glycol ether used as the component (c2) is preferably a mono-, di-, or triethylene glycol monoalkyl ether with an alkyl group having a carbon number of 1 to 8, preferably 2 to 6, mono, di, or tri Propylene Glycol Monoalkyl Ether. As (c2) component, diethylene glycol butyl ether is preferable.

The polypropylene glycol as the component (c3) is preferably polypropylene glycol having a weight average molecular weight of 500 or more, further 600 or more, further 700 or more, and further 5000 or less, further 3000 or less, further 2000 or less. As (c3) component, polypropylene glycol whose weight average molecular weight is 700-2000, for example, 1000 is preferable.

From the viewpoint of the sustainability of cleansing foam, (c) component is preferably (c1) component. The cleaning composition (I) for hard articles of this invention preferably contains (c1) component as (c) component from a viewpoint of the persistence of a cleansing foam.

From the viewpoint of the persistence of the cleansing foam, the cleaning composition (I) for hard articles of the present invention may contain, for example, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass % or more, and preferably 30 mass % or less, more preferably 20 mass % or less, still more preferably 10 mass % or less, still more preferably 8 mass % or less of the component (c).

Regarding the cleansing agent composition (I) for hard articles of the present invention, from the viewpoint of the persistence of the cleansing foam, the mass ratio of the content of the component (a) to the content of the component (c) is (a)/(c) 0.40 or more, preferably 0.50 or more, more preferably 0.60 or more, and 5.0 or less, preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less, still more preferably 2 or less, and still more It is preferably at most 1.5, more preferably at most 1.0, even more preferably at most 0.85, even more preferably at most 0.78.

When the cleansing agent composition (I) for hard articles of the present invention contains (c1) component as (c) component, from the viewpoint of the persistence of cleansing foam, (a)/(c) is 0.40 or more, Preferably at least 0.50, more preferably at least 0.60, and at most 5.0, preferably at most 4.0, more preferably at most 3.0, still more preferably at most 2.5, still more preferably at most 2.0, even more preferably at most 1.5 , and still more preferably 1.0 or less, still more preferably 0.85 or less, still more preferably 0.78 or less. When the cleanser composition (I) for hard articles of the present invention contains (c1) component as (c) component, from the viewpoint of the persistence of cleansing foam, the content of (a) component and (c1) component The mass ratio of the content (a)/(c1) is preferably 0.40 or more, more preferably 0.50 or more, and more preferably 0.60 or more, and is preferably 5.0 or less, more preferably 4.0 or less, and more preferably 3.0 or less, still more preferably 2.5 or less, still more preferably 2.0 or less, still more preferably 1.5 or less, still more preferably 1.0 or less, still more preferably 0.85 or less, still more preferably 0.78 or less.

Also, when the cleansing agent composition (I) for hard objects of the present invention contains (c2) component and/or (c3) component as the situation of (c) component, from the viewpoint of the persistence of the cleansing foam, (a )/(c) is preferably at least 0.60, more preferably at least 1.0, and at most 5.0, preferably at most 4.0, preferably at most 3.0, more preferably at most 2.0. When the cleanser composition (I) for hard objects of the present invention contains (c2) component and/or (c3) component as (c) component, from the viewpoint of the sustainability of the cleansing foam, (a) component The mass ratio (a)/[(c2)+(c3)] of the content of (c2) and the total content of (c3) is preferably 0.60 or more, more preferably 1.0 or more, and less than 5.0. Preferably it is 4.0 or less, more preferably 3.0 or less, more preferably 2.0 or less.

Also, when the cleansing agent composition (I) for hard objects of the present invention contains (c1) component, (c2) component and/or (c3) component as component (c), from the viewpoint of the persistence of the cleansing foam In other words, the mass ratio of the content of component (c1) to the total content of components (c2) and (c3) (c1)/[(c2)+(c3)] is preferably 0.1 or more, more preferably 0.3 or more , more preferably 0.6 or more, and 10 or less, preferably 6 or less, preferably 4 or less, more preferably 3 or less.

In the cleaning composition (I) for hard articles of the present invention, within the range that does not impair the purpose of the present invention, surfactants, enzymes (proteolytic enzymes) other than components (a) and (b) can be formulated. Enzymes, lipolytic enzymes, glycolytic enzymes, etc.), hydrotropes, pH value regulators, thickeners, dispersants, viscosity regulators, spices, colorants, antioxidants, preservatives and other ingredients.

The cleanser composition (I) for hard objects of the present invention optionally contains (d) component of more than one surfactant selected from betaine-type surfactants and amide-type nonionic surfactants. From the viewpoint of stability, the content of component (d) is 10% by mass relative to the total amount of surfactants in the composition, preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1.5% by mass % or less, the lower limit may be 0 mass % or more. The content of the component (d) of the cleaning composition (I) for hard objects of this invention may be 0 mass % in a composition.

(d) The betaine-type surfactant in the component is a surfactant having a betaine structure. Examples of betaine-type surfactants include alkyl (e.g., carbon number 8 to 18) dimethylaminoacetic acid betaine, alkyl (e.g., carbon number 8 to 18) amidopropyl betaine, Alkyl (for example, carbon number 8 to 18) hydroxy sultaine, alkyl (preferably carbon number 8 to 18) carboxymethyl hydroxyethyl imidazolium betaine and the like. In the present invention, the content of the betaine-type surfactant can be selected from alkyl (more than 8 and less than 18 carbons) betaine dimethylaminoacetate, alkyl (more than 8 and less than 18 carbons) amidopropyl Betaine, alkyl (carbon number 8 to 18) hydroxysulfobetaine, and alkyl (carbon number 8 to 18) carboxymethyl hydroxyethyl imidazolium betaine betaine-type surfactant in hard articles The total content in the detergent composition (I).

The amide-type nonionic surfactant in the component (d) may, for example, be an amide compound of a fatty acid having 8 or more and 18 or less carbon atoms and an alkylamine having 1 or more and 6 or less hydroxyl groups. The alkylamine is preferably an alkylamine having a carbon number of 1 or more, more preferably 2 or more, and 8 or less. Specifically, for example, monoethanolamine, diethanolamine, monopropanolamine, dipropanol Amines, reduced glucosamine, N-methylglucamine, N-methylethanolamine. In the present invention, fatty acid (carbon number 8 to 18) diethanolamide, fatty acid (carbon number 8 to 18) N-methylethanolamide and fatty acid (carbon number 8 to 18) N-methylethanolamide may be contained. - As (d) component, one or more amide-type nonionic surfactants of methylglucamide. In the present invention, the content of amide type nonionic surfactant can be selected from fatty acid (more than 8 and less than 18 carbon numbers) diethanolamide, fatty acid (more than 8 and less than 18 carbon numbers) N-methylethanolamide and The total content of the amide-type nonionic surfactant of N-methylglucamide fatty acid (carbon number 8 to 18) in the cleaning composition (I) for hard articles.

Regarding the cleansing agent composition (I) for hard articles of the present invention, from the viewpoint of the persistence of the cleansing foam, the total amount of the surfactant in the composition is, for example, preferably 1% by mass or more, more preferably 2.5% by mass Above, more preferably at least 5% by mass, more preferably at most 50% by mass, more preferably at most 40% by mass, further preferably at most 30% by mass. The detergent composition (I) for hard articles of the present invention is a composition containing a surfactant, and may also contain (a) component, (b) component, and optionally contain (d) component as a surfactant, and the interface A composition in which the total amount of active agent is within the above-mentioned range.

From the viewpoint of the stability and workability of the composition, the cleaning composition (I) for hard objects of the present invention preferably contains water. Water is not particularly limited, and examples thereof include tap water, well water, ion-exchanged water, and distilled water. In the present invention, water is preferably used in the balance of the composition (amount to 100% by mass in total). The content of water may be, for example, 50% by mass or more, furthermore, 60% by mass or more, and furthermore, 70% by mass or more in the cleaning composition (I) for hard articles. The cleaning composition (I) for hard articles of the present invention may be a liquid composition.

The pH value of the cleaning composition (I) for hard articles of the present invention at 20°C may be, for example, preferably 5 or more, more preferably 5.5 or more, further preferably 6 or more, and preferably 11 or less, more preferably 9 or less, more preferably 8.5 or less.

The cleaning composition (I) for hard articles of the present invention can be used for various hard articles, but is preferably used for tableware and/or hard articles around the kitchen, and is more preferably used for tableware.

Hard items around the kitchen are items used around the kitchen, specifically as follows: (1) Storage places for food, tableware and cooking utensils such as refrigerators and sideboards; (2) Food cooking places such as drainage tanks, countertops, range hoods, sinks, gas stoves, microwave ovens, etc.; and (3) Floors or walls around the above-mentioned storage place or the above-mentioned cooking place. In the present invention, these are referred to as "hard objects around the kitchen" for the sake of convenience. In addition, as tableware, specifically, the following components or utensils that are in contact with food materials can be cited: (i) so-called cutlery such as plates and bowls; (ii) Lunch boxes, bottles and other storage containers; (iii) Cooking utensils such as kitchen knives or chopping boards, pots, frying pans, grills; (iv) Cooking appliances such as food processors and blenders, etc. In the present invention, these are referred to as "tableware" for the sake of convenience. In addition, the present invention is preferably an object selected from tableware, storage containers, cooking utensils, and cooking appliances, more preferably objects selected from plates, bowls, bento boxes, bottles, kitchen knives, chopping boards, pans, and frying appliances. Items in pots, fish grills, food processors, and blenders are targeted.

The material of the hard object that is the object of the present invention can be, for example, plastic (including silicone resin, etc.), metal, pottery, wood, and combinations thereof. Moreover, the cleaning composition (I) for hard articles of the present invention can effectively clean oil stains adhering to these hard articles.

As mentioned above, oil stains attached to hydrophobic materials such as plastics become more difficult to remove due to modification, but in the present invention, even for oil stains attached to hard plastic objects, it also shows excellent cleaning effect, foam The durability is also excellent. The present invention is also suitable for cleaning hard objects made of plastic. Plastics can exemplify polyolefins such as polypropylene and polyethylene, polymethacrylate, polycarbonate, ABS (acrylonitrile-butadiene-styrene, acrylonitrile-butadiene-styrene) resin, polyethylene terephthalate Esters etc.

＜Cleaning method of hard objects (I)＞ The present invention provides a cleaning method (I) for a hard article in which the hard article cleaning composition (I) of the present invention is brought into contact with a hard article with dirt attached thereto. In the method (I) for cleaning hard objects of the present invention, the matters described in the cleaning composition (I) for hard objects of the present invention can be suitably applied.

In the cleaning method (I) for hard articles of the present invention, it is preferable to make the cleaning composition for hard articles (I) of the present invention foam and contact the hard articles. For example, the cleaning composition (I) for hard articles of the present invention may be foamed by, for example, a sponge or a spray device equipped with a foam forming mechanism, and brought into contact with hard articles.

The hard article which is the object of the cleaning method (I) of the hard article of this invention is mentioned in the cleaning composition (I) for hard articles of this invention. Tableware is one of the suitable hard items.

In the cleaning method (I) of the hard article of the present invention, the dirt attached to the hard article may be oily dirt, and further may be dirt including oily dirt.

In the present invention, hard articles, such as tableware, can be hand-washed with the above-mentioned cleaning composition (I) for hard articles of the present invention, and then rinsed with water. As a specific hand-washing method, the following method for cleaning hard objects can be exemplified, that is, hard objects such as tableware are attached to a flexible material using the cleaning solution of the hard surface cleaner composition (I) of the present invention. After hand washing, rinse with water. For example, make a flexible material such as a sponge containing water adhere to the hard surface cleaner composition (I) of the present invention and keep the cleaning solution, rub it with your hands several times while making it foam, and scrub hard objects such as tableware. In terms of high foamability and foam persistence, the total concentration of component (a) and component (b) in the cleaning solution held by the flexible material is preferably 1,000 ppm or more, more preferably 2,000 ppm or more, and preferably 70,000 ppm or less, more preferably 50,000 ppm or less, still more preferably 30,000 ppm or less. Add water to rinse after cleaning. For example, in the present invention, 3.3 to 133 parts by mass of rinsing water is used for 1 part by mass of the hard surface cleaner composition (I) used for cleaning, so that the bubbles can be fully disappeared, which can quickly Finish rinsing. The amount of the rinse water is about 2/3 to 1/10 of that in the case of using the conventional hand washing detergent composition.

Also, in the cleaning method (I) for hard articles of the present invention, the cleaning composition (I) for hard articles of the present invention is made into droplets or foams, preferably in foams, and can be mixed with attached Contact with hard objects such as oil stains. In this method, a spray device can be used. That is, in this invention, the cleaning agent for hard articles which filled the container equipped with the spray apparatus with the cleaning composition (I) for hard articles of this invention can be used. The present invention provides a cleaning agent for hard objects contained in a spray container, which is formed by filling the cleaning agent composition (I) for hard objects of the present invention into a container equipped with a spraying device.

The above-mentioned container equipped with a spray device in the cleaning agent for hard articles contained in a spray container of the present invention can be, for example, a manual spray device that does not use a propellant such as a trigger spray container and a pump spray container; Aerosols, etc. The above-mentioned container with a spray device is preferably a trigger sprayer that can spray or coat the contents in the form of droplets or foam, more preferably a trigger sprayer with a mechanism for spraying the contents in the form of droplets Or a trigger sprayer with a foam forming mechanism (foam forming mechanism).

In the cleaning agent for hard articles contained in a spray container of the present invention, when using a trigger sprayer equipped with a mechanism for spraying the cleaning composition (I) for hard articles of the present invention in the form of droplets, In order to facilitate spraying, or to avoid rough sprayed droplets, spray in a straight line, and the area that can be sprayed is very narrow, the nozzle diameter of the nozzle of the spray container equipped with the above composition is preferably 0.1 mm or more, more preferably 0.3 mm mm or more, preferably less than 2 mm, more preferably less than 1 mm. In the case of using a trigger-type sprayer equipped with a droplet-shaped spraying mechanism, the cleaning agent for hard objects contained in a spray container of the present invention is sprayed preferably at least 0.1 mL, more preferably 0.3 mL in one operation. More than mL, preferably less than 5 mL, more preferably less than 2 mL of the cleaning composition (I) for hard objects.

In the case of using a trigger-type sprayer equipped with a foam forming mechanism, the cleaning agent for hard articles contained in a spray container of the present invention is sprayed preferably at least 0.5 mL, more preferably at least 1 mL in one operation, and It is preferably less than 30 mL, more preferably less than 15 mL, and more preferably less than 5 mL of the cleaning composition (I) for hard objects.

<Cleansing composition for hard articles (II)> The mechanism of action of the effect of the present invention is not necessarily fully elucidated, but the applicant considers the following. Among the modified oil stains, the modified oil stains attached to cooking utensils or cooking equipment, etc. are highly modified due to heat history, etc. In order to peel off the object during cleaning, it is considered advantageous to use a cleaner with relatively high hydrophobicity . However, this kind of cleaning agent generally has low foaming performance, and when cleaning oil stains with a relatively low degree of modification such as tableware, the low-modified oil stains show foam-breaking properties, so the foaming performance is insufficient. decrease in volume and efficiency. Also, if foaming is considered in order to preferentially clean tableware with relatively hydrophilic dirt and less modification, the cleanability of kitchen counters and stoves with more highly modified dirt will decrease. In the case where the ( _ax ) component and (b _x ) component of the present invention are adsorbed to modified oil stains, etc., for example, via an alkyl group as a hydrophobic group, it is considered that the component (a _x ) is due to the alkylene oxide as a hydrophilic group. The addition molar number of the base part is small, so it adsorbs near the adsorption interface, or expands the adsorption in the horizontal direction relative to the adsorption interface at a position far away from the adsorption interface. (b _x ) is a hydrophilic group such as an oxyalkylene moiety Adsorbed with relative degrees of freedom in the vertical direction relative to the adsorption interface. The components (a _x ) and (b _x ) with such adsorption characteristics cannot meet the performance requirements for highly modified oils and low modified oils, even if the hydrophilicity and hydrophobicity are adjusted with a single structure. When the components (a _x ) and (b _x ) coexist, it is predicted that the density of the hydrophilic group near the hydrophobic group will be higher, and the hydrophilic region will have a broad molecular aggregate away from the dirt interface. When the molecules of this kind of surfactant are assembled in the whole cleaning system with a specific hydrophilic and lipophilic index, it is considered that it can effectively adsorb highly modified oil stains with relatively high hydrophobicity, and the structure of the hydrophilic part is also firm, so It can promote the stripping and dispersion of highly modified oil stains that are difficult to clean without reducing foaming properties. Also, since the hydrophilic group region is wide, it is considered that foamability does not decrease. Furthermore, the effect of the present invention is not limited to the mechanism of action shown here.

The component ( _ax ) is a polyoxyalkylene alkyl or alkenylamine having an alkyl or alkenyl group with 8 to 18 carbon atoms and an average added mole number of the oxyalkylene group being 1 to 5.

From the standpoint of detergency (hereinafter referred to as "detergency") for highly modified oils, the carbon number of the alkyl or alkenyl group contained in the component (a _x ) is 8 or more, preferably 10 or more, Moreover, it is 18 or less, preferably 16 or less. The group that the component ( _ax ) has is preferably an alkyl group. The oxyalkylene group is preferably an oxyalkylene group having 2 carbon atoms and/or an oxyalkylene group having 3 carbon atoms, ie, an oxyethylene group and/or an oxypropylene group, more preferably an oxyethylene group. The component ( _ax ) preferably contains an oxyethylene group as the oxyalkylene group. From the viewpoint of detergency, the average added mole number of the oxyalkylene group of the component ( _ax ) is 1 to 5, preferably 1.5 or more, more preferably 2 or more, and more preferably 4.5 or less, More preferably, it is 3 or less.

As the ( _ax ) component, for example, an alkylene group or an alkenyl group having 8 to 18 carbon atoms, and an alkylene oxide group having an average addition mole number of 1 to 5 to 5 monoamines is exemplified. into things.

As ( _ax ) component, the compound represented by following general formula ( _ax1 ) is mentioned, for example.

[Chem 2]

[In the formula, R is an alkyl or alkenyl group with a carbon number of 8 to 18, EO is an ethoxyl group, m and n are the average addition moles, and are independently numbers of 0 to 5, m and n The total is more than 1 and less than 5]

In the formula (a _x 1), the carbon number of R may be 8 or more, further 10 or more, and 18 or less, further 16 or less. R is preferably an alkyl group. The total of m and n is preferably at least 1.5, more preferably at least 2, and is preferably at most 4.5, more preferably at most 3.

The HLB of the component (a _x ) is not particularly limited as long as it does not deviate from the range of the overall hydrophilic-lipophilic index of the cleaning composition for hard articles (II) of the present invention, but from the viewpoint of ease of acquisition and cleanability of the modified oil For example, it is preferably 9 or more, more preferably 9.5 or more, and is preferably 14.2 or less, more preferably 13.0 or less. The HLB of the ( _ax ) component was proposed by Griffin. Furthermore, in the present invention, in the method of <the method for measuring the hydrophilic-lipophilic index of the cleaning agent composition for hard objects (II)> described in this specification, wherein the cleaning agent composition for hard objects (II) ) is replaced by a mixture containing the surfactant to be measured at a concentration of 5% by mass and the balance being water. The hydrophilic-lipophilic index measured can be regarded as the HLB obtained by the Griffin method. The same applies to HLB of other surfactants such as the (b _x ) component.

From the viewpoint of detergency, the cleaning composition (II) for hard articles of the present invention may contain, for example, 0.01 mass % or more, further 0.05 mass % or more, further 0.1 mass % or more, and 50 mass % or less, and further 30 mass % % or less, and further 15% by mass or less (a _x ) component.

From the viewpoint of detergency, the cleaning composition (II) for hard articles of the present invention may contain, for example, preferably 10% by mass or more, more preferably 20% by mass, relative to the total amount of surfactant in the composition. Above, more preferably at least 25% by mass, still more preferably at least 30% by mass, more preferably at most 95% by mass, more preferably at most 90% by mass, further preferably at most 85% by mass (a _x ) Element. The total amount of surfactant is the ( _ax ) component, (b _x ) component, any (c _x ) component contained in the composition, and any surfactant other than these, such as any (d _x ) Components, the total amount of content of any (d' _x ) component. The cleaning composition (II) for hard articles of the present invention is a composition containing a surfactant, and may also be a composition containing (a _x ) component and (b _x ) component as a surfactant.

The component (b _x ) is a nonionic surfactant (however, the component (a _x ) and the amide type nonionic surfactant are excluded).

Also, the component (b _x ) of the present invention is a nonionic surfactant having a hydrocarbon group preferably having 10 or more carbon atoms, more preferably 11 or more carbon atoms, and preferably 18 or less, more preferably 16 or less hydrocarbon groups.

Furthermore, in the present invention, one having a hydrocarbon group having 10 or more carbon atoms can be used as a nonionic surfactant. Therefore, the content of nonionic surfactants included in the total amount of surfactants in the composition, such as (b _x ) components, the following (d _x ) components, etc., can be nonionic surfactants having a hydrocarbon group with a carbon number of 10 or more. The content of the agent in the composition. For example, a nonionic compound having a hydrocarbon group with a carbon number of 9 or less may not be included in the total amount of surfactants in the composition as it does not belong to nonionic surfactants.

As (b _x ) component, (b _x 1) polyoxyalkylene alkyl ether [hereinafter referred to as (b _x 1) component], (b _x 2) alkyl (poly) glycoside [ Hereinafter, referred to as (b _x 2) component], (b _x 3) polyoxyalkylene fatty acid ester [hereinafter referred to as (b _x 3) component], (b _x 4) polyglycerin fatty acid ester [hereinafter , referred to as (b _x 4) component], and (b _x 5) (poly)oxyalkylene sorbitan fatty acid ester [hereinafter referred to as (b _x 5) component] more than one non-ionic surface activity agent. The component (b _x ) may be a nonionic surfactant selected from alkoxylate-type nonionic surfactants and alkylglycoside-type surfactants. The component (b _x 1) is an example of an alkoxylate type nonionic surfactant. Moreover, (b _x 2) component is an example of an alkyl glycoside type surfactant.

The oxyalkylene group of the component (b _x 1) is preferably an oxyalkylene group with 2 carbons and/or an oxyalkylene group with 3 carbons, namely oxyethylidene and/or oxypropylidene, more preferably Oxyethylene. From the viewpoint of detergency, the average added mole number of the oxyalkylene group of the component (b _x 1) is preferably 0 or more, more preferably 1 or more, and is preferably 25 or less, more preferably 23 or less . The component (b _x 1) preferably contains an oxyethylene group as the oxyalkylene group from the viewpoint of cleaning properties. From the viewpoint of detergency, the carbon number of the alkyl group of the component (b _x 1) is preferably 10 or more, more preferably 12 or more, and preferably 30 or less, more preferably 24 or less, and still more preferably 18 or less, and more preferably 16 or less. The alkyl group of the component (b _x 1) may be a straight chain or a branched chain, but is preferably a straight chain. The alkyl group of the component (b _x 1) may be saturated or unsaturated, but is preferably saturated.

Regarding the component (b _x 2), the carbon number of the alkyl group is preferably 10 or more, more preferably 12 or more, and preferably 30 or less, more preferably 24 or less, from the viewpoint of cleansing properties. 18 or less, more preferably 16 or less. Also, the average condensation degree of sugars such as glucose in the component (b _x 2) is preferably 1 or more and 10 or less, and more preferably 5 or less, from the viewpoint of cleansing properties. From the viewpoint of cleansing properties, the component (b _x 2) is preferably an alkyl (poly)glycoside whose structural sugar is glucose.

The cleaning composition (II) for hard articles of the present invention preferably contains at least one nonionic surfactant selected from (b _x 1) component and (b _x 2) component as (b _x ) component, and more It is preferable to contain one or more nonionic surfactants selected from the (b _x 1) component as the (b _x ) component.

The HLB of the component (b _x ) is not particularly limited as long as it does not deviate from the scope of the overall hydrophilic-lipophilic index of the cleaning agent composition for hard objects (II) of the present invention, but from the viewpoint of ease of acquisition and cleanability of the modified oil For example, it is preferably 9 or more, more preferably 9.5 or more, and is preferably 17.4 or less, more preferably 16.9 or less. The HLB of the component (b _x ) is obtained by the Griffin method. As mentioned above, the hydrophilic-lipophilic index measured by the prescribed method can be regarded as the HLB of the component (b _x ) obtained by the Griffin method HLB.

As for the component (b _x ), from the viewpoint of cleansing property, it is preferable that the HLB of at least one selected from alkoxylate-type nonionic surfactants and alkylglycoside-type surfactants is 9 or more and 17.4 or less. An ionic surfactant, more preferably a nonionic surfactant selected from one or more of the components (b _x 1) and (b _x 2) with an HLB of 9 to 17.4, more preferably selected from (b _x 1) One or more nonionic surfactants with an HLB of 9 to 17.4.

From the viewpoint of detergency, the cleaning composition (II) for hard articles of the present invention may contain, for example, preferably at least 0.01% by mass, more preferably at least 0.05% by mass, further preferably at least 1% by mass, and The (b _x ) component is preferably at most 30% by mass, more preferably at most 20% by mass, and still more preferably at most 10% by mass.

From the viewpoint of detergency, the cleaning composition (II) for hard articles of the present invention contains, for example, preferably at least 8% by mass, more preferably at least 10% by mass, relative to the total amount of surfactant in the composition. , more preferably at least 15% by mass, more preferably at least 20% by mass, more preferably at most 80% by mass, more preferably at most 75% by mass, further preferably at most 70% by mass, even more preferably at most 68% by mass Mass % or less (b _x ) component, further HLB of (b _x ) component of 9 to 17.4, further HLB of one or more selected from alkoxylate type nonionic surfactants and alkyl glycoside type surfactants It is a nonionic surfactant of 9 or more and 17.4 or less, and further selected from nonionic surfactants whose HLB of one or more of the components (b _x 1) and (b _x 2) is 9 or more and 17.4 or less, and further selected from (b x 2) components _x 1) Nonionic surfactants with one or more components having an HLB of 9 to 17.4.

Regarding the cleaning composition (II) for hard articles of the present invention, from the viewpoint of cleaning performance, the mass ratio of the content of the component (a _x ) to the content of the component (b _x ) is (a _x )/(b _x ) is, for example, preferably 0.01 or more, more preferably 0.04 or more, further preferably 0.08 or more, further preferably 0.1 or more, and preferably 30 or less, more preferably 20 or less, further preferably 13 or less, and further More preferably, it is 10 or less.

In the cleaning composition ₍ II) _for hard objects of the present invention, surfactants, solvents, Enzymes (proteolytic enzymes, lipolytic enzymes, glycolytic enzymes, etc.), hydrotropes, pH value regulators, thickeners, dispersants, viscosity regulators, fragrances, colorants, antioxidants, preservatives and other ingredients.

The cleaning composition (II) for hard articles of this invention may contain the following (c _x ) component arbitrarily. (c _x )Ingredient: anionic surfactant

Examples of the (c _x ) component include: fatty acid salt (preferably having 8 to 24 carbon atoms), alkyl (preferably having 8 to 24 carbon atoms) sulfonate, alkyl group (preferably having 8 to 24 carbon atoms) 8 to 18) benzene sulfonate, alkyl (preferably carbon number 8 to 24) sulfate ester salt, alkyl (preferably carbon number 2 to 24) phosphate ester salt, polyoxyalkylene ( Preferably polyoxyethylene) alkyl (preferably 8 to 18 carbons) sulfate ester salt, polyoxyethylene (preferably polyoxyethylene) alkyl (preferably 8 carbons) More than 18) carboxylate, alkyl (preferably 6 to 18 carbon number) sulfosuccinate, etc. Salts may, for example, be alkali metal salts such as sodium salts or potassium salts.

From the viewpoint of detergency, the cleaning composition (II) for hard articles of the present invention may contain, for example, preferably at least 0.01% by mass, more preferably at least 0.05% by mass, further preferably at least 0.1% by mass, and The (c _x ) component is preferably at most 5% by mass, more preferably at most 3.5% by mass, and still more preferably at most 2.4% by mass.

Regarding the cleaning composition (II) for hard articles of the present invention, from the viewpoint of cleaning performance, the content of the component (c _x ) is preferably 0% by mass relative to the total amount of the surfactant in the composition. More than 0.1% by mass, more preferably 0.5% by mass, more preferably 1% by mass, more preferably 3% by mass, more preferably 50% by mass or less, more preferably 25% by mass Mass % or less, More preferably, it is 22 mass % or less, More preferably, it is 20 mass % or less, Still more preferably, it is 18.5 mass % or less. The content of the component (c _x ) in the cleaning composition (II) for hard articles of the present invention may be 0% by mass in the composition.

The cleaning composition (II) for hard articles of the present invention may optionally contain the following (d _x ) component. From the viewpoint of cleaning performance, the content of (d _x ) component is relative to the total amount of surfactant in the composition It is preferably less than 10 mass %, more preferably 2 mass % or less, further preferably 1 mass % or less, further preferably 0.5 mass % or less, and the lower limit may be 0 mass % or more. The content of the component (d _x ) in the cleaning composition (II) for hard articles of the present invention may be 0% by mass in the composition. (d _x ) component: amide type nonionic surfactant

The component (d _x ) may, for example, be an amide compound of a fatty acid having a carbon number of 8 or more, and furthermore, a fatty acid having 11 or more and 18 or less, and an alkylamine having 1 or more and 6 or less hydroxyl groups. The alkylamine is preferably an alkylamine having 1 or more carbon atoms, and furthermore, an alkylamine having 2 or more and 8 or less carbon atoms. Specifically, for example, monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, Reduced Glucosamine, N-Methylglucamine, N-Methylethanolamine. In the present invention, it may contain fatty acid (the carbon number is more than 8, further 11 to 18) diethanolamide, fatty acid (carbon number is 8 or more, further 11 to 18) N-methylethanolamide and Fatty acid (with carbon number of 8 or more, further 11 or more and 18 or less) N-methylglucamide is used as the (d _x ) component. In the present invention, the content of the component (d _x ) can be selected from fatty acids (with a carbon number of 8 or more, further ranging from 11 to 18) diethanolamide, fatty acids (with a carbon number of 8 or more, further ranging from 11 to 18) ) Total content of N-methylethanolamide and fatty acid (with carbon number of 8 or more, further 11 or more and 18 or less) N-methylglucamide amide-type nonionic surfactant in the composition.

The cleaning composition (II) for hard objects of the present invention may optionally contain the following (d' _x ) component. From the viewpoint of cleaning performance, the content of (d' _x ) component is relative to the surfactant in the composition The total amount is preferably less than 10 mass %, more preferably 5 mass % or less, further preferably 3 mass % or less, further preferably 1.5 mass % or less, and the lower limit may be 0 mass % or more. The content of the component (d' _x ) of the cleaning composition (II) for hard articles of the present invention may be 0% by mass in the composition. (d' _x )Ingredient: betaine type surfactant

The component (d' _x ) is a surfactant having a betaine structure. Examples of the (d' _x ) component include: alkyl (e.g., carbon number 8 to 18) dimethylaminoacetate betaine, alkyl (e.g., carbon number 8 to 18) amidopropyl betaine, Alkyl (for example, carbon number 8 to 18) hydroxy sultaine, alkyl (preferably carbon number 8 to 18) carboxymethyl hydroxyethyl imidazolium betaine and the like. In the present invention, the content of the component (d' _x ) can be selected from the group consisting of alkyl (8 to 18 carbons) dimethylaminoacetate betaine, alkyl (8 to 18 carbons) amidopropyl Betaine, alkyl (carbon number 8 to 18) hydroxysulfobetaine, and alkyl (carbon number 8 to 18) carboxymethyl hydroxyethyl imidazolium betaine betaine-type surfactant in the composition The total content in it.

Regarding the cleaning composition (II) for hard objects of the present invention, the total amount of surfactant in the composition is, for example, preferably 0.1% by mass or more, more preferably 1% by mass, from the viewpoint of cleaning performance and workability more than 2.5% by mass, more preferably at least 5% by mass, more preferably at least 8% by mass, more preferably at most 50% by mass, more preferably at most 40% by mass, and still more preferably at least 50% by mass. 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less. The detergent composition (II) for hard articles of the present invention may be a composition containing a surfactant, or may contain (a _x ) component and (b _x ) component as a surfactant, and the total amount of the surfactant is between A composition within the above range.

The cleaning composition (II) for hard articles of the present invention may optionally contain the following ( _ex ) component, but since the ( _ex ) component has a tendency to increase the hydrophilic and hydrophobic index of the composition, there is a risk of affecting the cleaning performance , so care needs to be taken when including it. Regarding the cleaning composition (II) for hard articles of the present invention, the content of the component ( _ex ) is preferably less than 50% by mass relative to the total amount of surfactants in the composition from the viewpoint of cleaning performance. It is further preferably 10 mass % or less, further preferably 5 mass % or less, further preferably 3 mass % or less, further preferably 2 mass % or less, and the lower limit may be 0 mass % or more to adjust the combination For the purpose of viscosity and other properties of the substance, it may be 0.5% by mass or more, and further may be 0.1% by mass or more. The content of the ( _ex ) component of the cleaning composition (II) for hard objects of this invention may be 0 mass % in a composition. ( _ex ) Component: A hydrophilic solvent having a hydrocarbon group having 9 or less carbon atoms and having a solubility in water of 5 g/100 g or more at 25°C

As the ( _ex ) component, there may be exemplified monohydric alcohols, diols, triols, mono-/di- or tri-alkylene glycol monoethers, and mono-/di- or tri-alkylene diols. One or more hydrophilic solvents such as alcohol diether. The component ( _ex ) may, for example, have an alkyl group. The alkyl group can be selected from alkyl groups of various carbon numbers. The carbon number of the alkyl group is preferably 1 or more, more preferably 3 or more, and is preferably less than 10, more preferably 8 or less. The ( _ex ) component is preferably selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1,2-hexanediol, One or more of ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether The hydrophilic solvent is more preferably one or more hydrophilic solvents selected from ethanol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether, and more preferably diethyl ether Diol Monobutyl Ether.

From the viewpoint of the stability and workability of the composition, the cleaning composition (II) for hard objects of the present invention preferably contains water. Water is not particularly limited, and examples thereof include tap water, well water, ion-exchanged water, and distilled water. In the present invention, water is preferably used in the balance of the composition (amount to 100% by mass in total). The content of water may be, for example, 50% by mass or more, furthermore, 60% by mass or more, and furthermore, 70% by mass or more in the cleaning composition (II) for hard articles. The cleaning composition (II) for hard articles of the present invention may be a liquid composition.

The cleansing agent composition (II) for hard objects of this invention has the hydrophilic-lipophilic index of the composition whole from the viewpoint of cleansing property to 9-14.2. Regarding the hydrophilic-lipophilic index of the cleaning agent composition (II) for hard objects of the present invention, from the viewpoint of cleaning performance, for example, it can be 9 or more, preferably 9.5 or more, more preferably 9.6 or more, and more preferably 9.6 or more. 9.7 or more, more preferably 9.8 or more, still more preferably 9.9 or more, more preferably 10 or more, still more preferably 10.0 or more, and 14.2 or less, preferably 14.0 or less, more preferably 13.9 or less, still more preferably 13.8 or less, more preferably 13.7 or less, still more preferably 13.6 or less, still more preferably 13.5 or less, still more preferably 13.4 or less, still more preferably 13.3 or less, still more preferably 13.2 or less, still more preferably 13.2 or less 12 or less, more preferably 12.0 or less, still more preferably 11 or less, still more preferably 11.0 or less. In the present invention, the hydrophilic-lipophilic index of the cleaning composition (II) for hard articles of the present invention is measured by the following method. This measurement method is based on the knowledge described in Japanese Patent Laid-Open No. 2020-38061, that is, an oil component and a probe for phase change can be added to an aqueous sample, and the phase structure of the mixture can be changed according to the phase structure of the mixture. The physical properties of aqueous samples containing surfactants and water were estimated by varying the amount of probes.

<Measurement method of the hydrophilic and lipophilic index of the cleaning composition (II) for hard articles> (1) Preparation of calibration curve A plurality of polyoxyethylene lauryl ethers having different HLB values of Griffin were prepared. When the concentration (mmol/kg, the same applies hereinafter) of the surfactant in the cleaning composition for hard objects to be measured is unknown, the concentration is measured first. Mix water and polyoxyethylene lauryl ether (of the prescribed HLB) to prepare a precursor sample in which the concentration of polyoxyethylene lauryl ether is the same as that of the surfactant in the cleaning composition for hard objects. Add 2 g of oil (isoalkane with an average carbon number of 16) and 5 g of solvent (diethylene glycol butyl ether) to the precursor sample to make a standard sample, and add a phase change probe (diethylene glycol butyl ether) to the standard sample. Glycol Monooctyl Ether) quantifies the amount of probe required for phase transition before the phase structure of the standard sample changes. The quantification of multiple polyoxyethylene lauryl ethers with different HLB values is carried out under the same conditions to obtain multiple quantitative values, based on the quantitative values and the HLB value of the surfactant contained in the standard sample that gives the quantitative values Make a calibration curve. (2) Calculation of hydrophilic and lipophilic index A measurement sample was prepared by adding 2 g of oil (isoalkane with an average carbon number of 16) and 5 g of a solvent (diethylene glycol butyl ether) to the cleaning composition for hard articles. A phase change probe (diethylene glycol monooctyl ether) was added to the measurement sample, and the amount of the phase change probe required before the phase structure of the measurement sample changed was quantified. The quantitative value of the probe for measuring the phase transition of the sample is applied to the calibration curve, and the HLB value of the corresponding calibration curve is used as the hydrophilic-lipophilic index of the cleaning composition for hard articles. In addition, in each operation of said (1) and (2), the temperature of each sample was set to 25 degreeC, respectively.

The hydrophilic and lipophilic index of the cleaning composition (II) for hard objects of the present invention can be set within a predetermined range by adjusting the (a _x ) component, (b _x ) component, the type or the amount of the optional component, etc. . In the present invention, in order to make the hydrophilicity index within a predetermined range, for example, the following methods are suitably employed alone or in combination. 1: Adjust the mass ratio of (a _x )/(b _x ) components. Regarding the mass ratio of the (a _x )/(b _x ) component, for example, as described above, it is preferably at least 0.01, more preferably at least 0.04, still more preferably at least 0.08, and still more preferably at least 0.08. It is 0.1 or more, and is preferably 30 or less, more preferably 20 or less, still more preferably 13 or less, and still more preferably 10 or less. 2: Adjust the content of component (c _x ) as a hydrophilic surfactant. Regarding the content of the component (c _x ), for example, as described above, it is preferably at least 0% by mass, more preferably at least 0.1% by mass, and still more preferably at least 0% by mass based on the total amount of surfactant in the composition 0.5% by mass or more, more preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 50% by mass or less, more preferably 25% by mass or less, Furthermore, it is more preferable to set it as 22 mass % or less, still more preferably, it is 20 mass % or less, and it is still more preferable to set it as 18.5 mass % or less. 3: Adjust the content of (d' _x ) component as a hydrophilic surfactant. Regarding the content of the component (d' _x ), for example, as described above, it is less than 10% by mass, further 5% by mass or less, further 3% by mass or less, based on the total amount of the surfactant in the composition, Furthermore, it shall be 1.5 mass % or less, and shall be 0 mass % or more, or the content of (d' _x ) component in a composition shall be 0 mass %. 4: Adjust the content of hydrophobic surfactants, such as (d _x ) components. Regarding the content of the component (d _x ), for example, as described above, it is less than 10% by mass, further 2 mass% or less, further 1 mass% or less, and further It is 0.5 mass % or less, and it is 0 mass % or more, or the content of (d _x ) component in a composition is 0 mass %. 5: Adjust the content of ( _ex ) component. As mentioned above, the content of the component ( _ex ) is less than 50% by mass, further 10% by mass or less, further 5% by mass or less, and furthermore, relative to the total amount of the surfactant in the composition, as described above. 3 mass % or less, further 2 mass % or less, further 0 mass % or more, further 0.1 mass % or more, further 0.5 mass % or more, or ( _ex ) component in the composition The content was set to 0% by mass.

Regarding the cleaning composition (II) for hard articles of the present invention, from the viewpoint of cleaning performance, the pH value at 20° C. is, for example, preferably 5 or higher, more preferably 5.5 or higher, and still more preferably 6 or higher , and is preferably 11 or less, more preferably 9 or less, further preferably 8.5 or less.

The cleaning composition (II) for hard articles of the present invention can be used for various hard articles, but is preferably used for tableware and/or hard articles around the kitchen, and is more preferably used for tableware.

Hard items around the kitchen are items used around the kitchen, specifically as follows: (1) Storage places for food, tableware and cooking utensils such as refrigerators and sideboards; (2) Food cooking places such as drainage tanks, countertops, range hoods, sinks, gas stoves, microwave ovens, etc.; and (3) Floors or walls around the above-mentioned storage place or the above-mentioned cooking place. In the present invention, these are referred to as "hard objects around the kitchen" for the sake of convenience. In addition, as tableware, specifically, the following components or utensils that are in contact with food materials can be cited: (i) so-called cutlery such as plates and bowls; (ii) Lunch boxes, bottles and other storage containers; (iii) Cooking utensils such as kitchen knives or chopping boards, pots, frying pans, grills; (iv) Cooking appliances such as food processors and blenders, etc. In the present invention, these are referred to as "tableware" for the sake of convenience. In addition, the present invention preferably targets items selected from tableware, storage containers, cooking utensils, and cooking appliances, more preferably objects selected from plates, bowls, bento boxes, bottles, kitchen knives, chopping boards, pans, and frying appliances. Items in pots, fish grills, food processors, and blenders are targeted.

The material of the hard object that is the object of the present invention can be, for example, plastic (including silicone resin, etc.), metal, pottery, wood, and combinations thereof. Moreover, the cleaning composition (II) for hard articles of the present invention can effectively clean oil stains adhering to these hard articles.

As mentioned above, modified oil stains attached to hydrophobic materials such as plastics are difficult to remove. However, in the present invention, even modified oil stains attached to plastic hard objects have excellent cleaning effects. The present invention is also suitable for cleaning hard objects made of plastic. Examples of plastics include polyolefins such as polypropylene and polyethylene, polymethacrylate, polycarbonate, ABS resin, polyethylene terephthalate, and the like.

＜How to clean hard objects (II)＞ The present invention provides a cleaning method (II) for a hard article in which the hard article cleaning composition (II) of the present invention is brought into contact with a hard article with dirt attached thereto. In the cleaning method (II) for hard articles of the present invention, the matters described in the cleaning composition (II) for hard articles of the present invention can be suitably applied.

In the cleaning method (II) for hard articles of the present invention, the cleaning composition (II) for hard articles of the present invention may be foamed and brought into contact with hard articles. For example, the cleaning composition (II) for hard articles of the present invention can be foamed by, for example, a sponge or a spray device equipped with a foam forming mechanism, and brought into contact with hard articles. In addition, the hard article cleaning composition (II) of the present invention can be brought into contact with hard articles by spraying, coating, immersion, or the like.

The hard article which is the object of the cleaning method (II) of the hard article of this invention is mentioned in the cleaning composition (II) for hard articles of this invention. Tableware is one of the suitable hard items.

In the cleaning method (II) of the hard article of the present invention, the dirt adhering to the hard article may be oil stains such as modified oil stains, and further may be modified oil stains.

In the cleaning method (II) of the hard article of the present invention, the hard article to which oil stains including modified oil, especially thermally modified oil, etc. are attached can be dipped in the above-mentioned composition to make it contact with the hard article of the present invention. Detergent composition (II), but from the viewpoint of efficiently improving the cleaning power, it is preferable to spray or apply the above-mentioned composition so that it is mixed with oil stains containing modified oil, especially thermally modified oil, etc. The method of contacting the attached hard object. The method of bringing the cleaning composition (II) for hard articles of the present invention into contact with hard articles with oil stains etc. is preferably spraying or coating, more preferably spraying in droplet form or coating in foam form. Regarding the contact of the hard article cleaning composition (II) for hard articles of the present invention, specifically, for example, a spray device is used. That is, in this invention, it is preferable to use the cleaning agent for hard articles which filled the container equipped with the spray apparatus with the cleaning composition (II) for hard articles of this invention.

As the method of foam coating, for example, the method of entraining air in the nozzle part of the spray device for hard articles (II) of the present invention and foaming; by making the hard articles of the present invention A method in which the detergent composition (II) is contained in a sponge or a cleaning fiber article, etc., and rubbed several times to make it foam.

The present invention provides a cleaning agent for hard objects of the present invention contained in a spray container, which is formed by filling the cleaning agent composition (II) for hard objects of the present invention into a container equipped with a spraying device.

The above-mentioned container equipped with a spray device in the cleaning agent for hard articles contained in a spray container of the present invention can be, for example, a manual spray device that does not use a propellant such as a trigger spray container and a pump spray container; Aerosols, etc. The above-mentioned container with a spray device is preferably a trigger sprayer that can spray or coat the contents in the form of droplets or foam, more preferably a trigger sprayer with a mechanism for spraying the contents in the form of droplets Or a trigger sprayer with a foam forming mechanism (foam forming mechanism).

In the cleaning agent for hard objects contained in a spray container of the present invention, when using a trigger sprayer equipped with a mechanism for spraying the cleaning agent composition (II) for hard objects of the present invention in the form of droplets, In order to spray easily, or to avoid rough sprayed droplets, spray in a straight line, and the area that can be sprayed is very narrow, the nozzle diameter of the nozzle of the spray container equipped with the above composition is preferably 0.1 mm or more, more preferably 0.3 mm mm or more, preferably less than 2 mm, more preferably less than 1 mm. In the case of using a trigger-type sprayer equipped with a droplet-shaped spraying mechanism, the cleaning agent for hard objects contained in a spray container of the present invention is sprayed preferably at least 0.1 mL, more preferably 0.3 mL in one operation. More than mL, preferably less than 5 mL, more preferably less than 2 mL.

In the case of using a trigger-type sprayer equipped with a foam forming mechanism, the cleaning agent for hard articles contained in a spray container of the present invention is sprayed preferably at least 0.5 mL, more preferably at least 1 mL in one operation, and The composition is preferably less than 30 mL, more preferably less than 15 mL, and still more preferably less than 5 mL.

In the cleaning method (II) of the hard article of this invention, the cleaning composition (II) for hard articles of this invention is brought into contact with a hard article, and it cleans. In the cleaning method (II) for hard articles of the present invention, for example, it can be immersed in the cleaning composition (II) for hard articles of the present invention, left in a coated state, wiped with a sponge or fiber product, and rinsed with running water , by which dirt is stripped and cleaned from hard objects. Furthermore, after that, it can be washed with running water or the like. The cleaning method (II) for hard articles of the present invention can be a hand-washing cleaning method, and hard articles such as tableware can be hand-washed and cleaned according to known methods.

Example The cleaning composition for hard objects in Tables 1-3 was prepared using the following ingredients, and the cleaning power on oily stains was evaluated according to the following method. The results are shown in Tables 1-3. The adjustment amount in the table means the amount used to adjust the pH value of the composition to the value in the table. Also, the (d)/surfactant total amount (mass %) in the table is the mass % of the content of (d) component relative to the surfactant total amount in the composition, the (d) of the composition of table 1,2 )/surfactant total amount is 0% by mass.

＜Preparation ingredients＞ (a) Ingredients ・AMIET 102: Polyoxyethylene laurylamine, average added molar number of oxyethylene groups 2.1, HLB 9.1 (equivalent to measured value by Griffin method*1), Kao Co., Ltd., AMIET 102 ・AMIET 302: Polyoxyethylene stearylamine, the average added molar number of oxyethylene groups is 2.1, HLB 7.4 (equivalent to measured value by Griffin method*1), Kao Co., Ltd., AMIET 302 ・AMIET 105: Polyoxyethylene laurylamine, average addition molar number of oxyethylene groups 4.2, HLB 10.4 (Griffin method equivalent measured value*1), Kao Co., Ltd., AMIET 105

(b) Ingredients (b1) Ingredients ・AG-124: Alkyl polyglucoside, HLB 11.5 (Griffin method equivalent measured value*1), Kao Co., Ltd., AG-124 ・E120: Polyoxyethylene lauryl ether, average added molar number of oxyethylene groups 13.2, HLB 15.3 (Griffin method*2), Kao Co., Ltd., Emulgen 120 ・E707: Polyoxyethylene alkyl ether, average addition molar number of oxyethylene groups 7, HLB 12.1 (Griffin method*2), Kao Co., Ltd., Emulgen 707

(b2) Ingredients ・Emal 20C: Polyoxyethylene sodium lauryl sulfate, the average added molar number of oxyethylene groups is 3, HLB 13.4 (equivalent to measured value by Griffin method*1), Kao Co., Ltd., Emal 20C ・Neopelex G-25: Sodium dodecylbenzenesulfonate, HLB 11.6 (Griffin method equivalent measured value*1), Kao Corporation, Neopelex G-25

(b') component (comparative component of (b) component) ・Quartamin 60W: Hexadecyltrimethylammonium chloride 30% aqueous solution, HLB 13.8 (equivalent to measured value by Griffin method*1), Kao Co., Ltd., Quartamin 60W, the addition amount in the table is based on cetyl Value in terms of trimethylammonium chloride

*1 The HLB equivalent to the measured value by the Griffin method is measured by the following method. A plurality of polyoxyethylene lauryl ethers having different HLB values of Griffin were prepared. Using the components to be measured and water, a composition having a surfactant concentration of 5% by mass was prepared, and the molar concentration (mmol/kg) of the surfactant was calculated. Mix water and polyoxyethylene lauryl ether (with specified HLB) to prepare a precursor sample with the same concentration of polyoxyethylene lauryl ether as the molar concentration of the above-mentioned surfactant. Add 2 g of oil (isoalkane with an average carbon number of 16) and 5 g of solvent (diethylene glycol butyl ether) to the precursor sample to make a standard sample, and add a phase change probe (diethylene glycol butyl ether) to the standard sample Alcohol Monooctyl Ether) to quantify the amount of probe required for phase transition before the phase structure of the standard sample changes. The quantification of polyoxyethylene lauryl ethers with different HLB values was performed under the same conditions to obtain a plurality of quantitative values, and a calibration curve was prepared based on the quantitative values and the HLB value of the polyoxyethylene lauryl ethers that gave the quantitative values. A measurement sample was prepared by adding 2 g of oil (isoalkane with an average carbon number of 16) and 5 g of a solvent (diethylene glycol butyl ether) to a surfactant composition obtained from the components to be measured and water. A phase change probe (diethylene glycol monooctyl ether) was added to the measurement sample, and the amount of the phase change probe required before the phase structure of the measurement sample changed was quantified. The quantitative value of the probe for measuring the phase transition of the sample is applied to the calibration curve, and the HLB value of the corresponding calibration curve is set as the HLB of the Griffin method equivalent value of the component to be measured. *2 The HLB based on the Griffin method is a calculated value using the average added moles of oxyethylene groups.

(c) Ingredients ・GE-EH: 2-Ethylhexyl monoglyceryl ether ・BDG: Diethylene glycol butyl ether ・PPG-1000: Polypropylene glycol, weight average molecular weight 1000

(d) ingredients ・Amide-type nonionic surfactant: Kao Co., Ltd., AMINON PK-02S, palm kernel oil fatty acid diethanolamide ・Betaine-type surfactants: Kao Corporation, Amphitol 20HD, Lauryl Hydroxysultaine

＜Continuity of Cleansing Foam＞ Spread 1 g of oil stain (tallow/rapeseed oil=1/1, mass ratio) on a pottery dish (23 cm in diameter). After the oil stain was applied, the pottery dish was left at 25° C. for 2 hours, and it was used as a stained dish for evaluation. Prepare a plurality of contamination plates for evaluation. A sponge (manufactured by KIKULON Co., Ltd.) was impregnated with 1 g of the cleaning composition for hard articles and 30 g of tap water (30° C.) and rubbed several times to make it foam, and then the stained plate for evaluation was cleaned. After cleaning, the state where there is no sticky feeling when touched with fingers is regarded as cleaning completion. After cleaning was complete, the sponge was not replaced (nor dipped in a new composition), it was lathered again, a new evaluation soiled dish was cleaned, and the cleaning was repeated until the cleaning could no longer be completed. The persistence of the cleansing foam was evaluated by the number of soiled dishes for evaluation that could complete the cleaning with foaming.

[Table 1] Example comparative example 1a-1 1a-2 1a-3 1a-4 1a-5 1a-6 1a-7 1a-8 1a-9 1a-1 1a-2 1a-3 1a-4 Cleaner composition for hard objects Deployment ingredients︵mass%︶ (a) AMIET 102 6 4 2 4 4 4 4 3 2 4 4 4 (b) AG-124 6 8 10 8 8 6 5 8 8 8 8 (b') Quartamin 60W 8 (c) GE-EH 3 3 3 5 7 5 6 4 5 3 3 3 citric acid Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount water margin margin margin margin margin margin margin margin margin margin margin margin margin total 100 100 100 100 100 100 100 100 100 100 100 100 100 (a)/(b) (mass ratio) 1 0.5 0.2 0.5 0.5 0.67 0.8 0.38 0.25 0 - 0.5 0.5 (a)/(c) (mass ratio) 2.0 1.3 0.67 0.80 0.57 0.80 0.67 0.75 0.40 0 1.3 - 1.3 pH value(20℃) 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 Exterior cloudy cloudy cloudy cloudy cloudy cloudy cloudy cloudy cloudy cloudy separate transparent transparent Sustainability of cleansing foam (cleaning quantity) 4 4 6 5 5 4 4 6 5 3 0 3 2

[Table 2] Example 2a-1 2a-2 2a-3 2a-4 2a-5 2a-6 2a-7 2a-8 Cleaner composition for hard objects Deployment ingredients︵mass%︶ (a) AMIET 102 4 4 4 4 4 4 AMIET 302 4 AMIET 105 4 (b) (b1) AG-124 8 8 8 8 E120 8 E707 8 (b2) Emal 20C 8 Neopelex G-25 8 (c) GE-EH 3 3 3 3 3 3 BDG 3 PPG-1000 3 citric acid Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount water margin margin margin margin margin margin margin margin total 100 100 100 100 100 100 100 100 (a)/(b) (mass ratio) 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 (a)/(c) (mass ratio) 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 pH value(20℃) 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 Exterior transparent transparent cloudy transparent transparent transparent gel cloudy Sustainability of cleansing foam (cleaning quantity) 5 5 5 6 5 5 7 4

[table 3] Example comparative example Example comparative example Example comparative example 3a-1 3a-1 3a-2 3a-2 3a-3 3a-3 Cleaner composition for hard objects Deployment ingredients︵mass%︶ (a) AMIET 102 4.0 4.0 4.0 4.0 4.0 4.0 (b) (b1) AG-124 8.0 8.0 8.0 8.0 8.0 8.0 (c) BDG 3.0 11 GE-EH 5 5 5 5 (d) Amide type nonionic surfactant 2 Betaine Surfactant 1 5 citric acid Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount water margin margin margin margin margin margin total 100 100 100 100 100 100 (a)/(c) (mass ratio) 1.3 0.36 0.80 0.80 0.80 0.80 (d)/surfactant total amount (mass %) 0.00 0.00 0.00 14 7.7 29 (a)/(b) (mass ratio) 0.50 0.50 0.50 0.50 0.50 0.50 pH value(20℃) 7.1 7.1 7.1 7.1 7.1 7.1 Exterior transparent transparent cloudy cloudy transparent transparent Sustainability of cleansing foam (cleaning quantity) 5 2 4 2 5 3

＜Adjustment example＞ In Table 4, the formulation example of the cleaning composition (I) for hard objects of this invention is shown.

[Table 4] Deployment example 4a-1 4a-2 4a-3 4a-4 4a-5 4a-6 4a-7 4a-8 4a-9 4a-10 4a-11 Cleaner composition for hard objects Deployment ingredients︵mass%︶ (a) AMIET 102 2 2 2 2 2 2 2 2 4 4 4 (b) (b1) AG-124 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 8 8 8 (c) (c1) GE-EH 1 1 1.5 2 3 1 3.5 0.5 3 3 3 (c2) BDG 1 0.5 0.5 1 1.5 0.5 3 (c3) PPG-1000 1 1 1.5 0.5 (d) Amide type nonionic surfactant 0.5 0.3 0.1 citric acid Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount water margin margin margin margin margin margin margin margin margin margin margin total 100 100 100 100 100 100 100 100 100 100 100 (a)/(b) (mass ratio) 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 (a)/(c) (mass ratio) 1.0 1.0 1.0 0.80 0.40 0.50 0.44 0.57 1.3 1.3 1.3 (a)/(c1) (mass ratio) 2.0 2.0 1.3 1.0 0.67 2.0 0.57 4.0 1.3 1.3 1.3 (a)/[(c2)+(c3)] (mass ratio) 2.0 2.0 4.0 4.0 1.0 0.67 2.0 0.67 - - - (c1)/[(c2)+(c3)] (mass ratio) 1.0 1.0 3.0 4.0 1.5 0.33 3.5 0.17 - - - (d)/surfactant total amount (mass %) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 4 2.4 0.83 pH value(20℃) 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1

The cleaning compositions for hard objects in Tables 5-7 were prepared using the following ingredients, and the cleaning performance on modified oil stains was evaluated according to the following method. The results are shown in Tables 5-7. The hydrophilic-lipophilic index in the table is the value of the whole composition measured at 25° C. by the above-mentioned method. In addition, the adjustment amount in a table|surface means the quantity for adjusting the pH value of a composition to the value in a table|surface.

＜Compounding ingredients＞ (a _x ) Components・AMIET 102: Polyoxyethylene laurylamine, average addition molar number of oxyethylene groups 2.1, HLB 9.1 (Griffin method equivalent measured value*1), Kao Co., Ltd. , AMIET 102

(b _x ) Components ・E102-KG: Polyoxyethylene lauryl ether, average addition molar number of oxyethylene groups 2, HLB 6.42 (Griffin method*2), Kao Co., Ltd., Emulgen 102KG ・E105: Polyoxyethylene lauryl ether, average addition molar number of oxyethylene 3.8, HLB 9.7 (Griffin method*2), Kao Co., Ltd., Emulgen 105 ・E108: Polyoxyethylene lauryl ether, oxyethylene The average added molar number of 5.6, HLB 12.1 (Griffin method *2), Kao Co., Ltd., Emulgen 108 ・E120: Polyoxyethylene lauryl ether, the average added molar number of oxyethylene 13.2, HLB 15.3 (Griffin method *2), Kao Co., Ltd., Emulgen 120 E121: polyoxyethylene lauryl ether, the average addition molar number of oxyethylene 21, HLB 16.65 (Griffin method *2), Kao Co., Ltd., Emulgen 121 E705: polyoxyethylene alkyl ether, the average addition molar number of oxyethylene is 5, the alkyl is a secondary alkyl with 11 to 15 carbons, HLB 10.5 (Griffin Method *2), Kao Co., Ltd., Emulgen 705 E707: polyoxyethylene alkyl ether, the average addition molar number of oxyethylene is 7, the alkyl is a secondary alkyl with 11 to 15 carbons, HLB 12.1 (Griffin method*2), Kao Co., Ltd., Emulgen 707 ・AG-124: Alkyl polyglucoside, the alkyl group is a primary alkyl group with 12-16 carbon atoms, the average sugar condensation degree is 1-2, HLB 11.5 (Griffin method equivalent measured value*1), Kao Co., Ltd., AG-124

(c _x ) Components ・Emal 20C: Polyoxyethylene sodium lauryl sulfate, average addition molar number of oxyethylene groups 3, HLB 13.4 (Griffin method equivalent measured value*1), Kao Co., Ltd. , Emal 20C

(d _x ) Components ・Amide-type nonionic surfactant: Kao Co., Ltd., AMINON PK-02S, palm kernel oil fatty acid diethanolamide

(d' _x ) Components ・Betaine-type surfactants: Kao Corporation, Amphitol 20HD, Lauryl Hydroxysultaine

( _ex ) Ingredients ・Diethylene glycol butyl ether: easily soluble in water (solubility in water is 5 g/100 g or more at 25°C)

*1 The actual measured value of the Griffin method refers to the hydrophilic and lipophilic index of each surfactant measured by <Method for Determination of Hydrophilic and Lipophilic Index of Cleaner Composition for Hard Objects> recorded in this manual, and its measurement is based on A mixture containing the surfactant to be measured at a concentration of 5% by mass and the balance being water was used as a cleaning composition for hard articles at 25°C. *2 The HLB based on the Griffin method is a calculated value using the average added moles of oxyethylene groups.

＜Cleaning power against modified oil stains＞ Peel off the protective film of SUS (Steel Use Stainless, Japan Stainless Steel Standard) 304 test piece (1.0 mm×25 mm×70 mm) manufactured by Engineering Test Service Co., Ltd., and use neutral tableware Clean and rinse the sponge with lotion (1 time with tap water, 2 times with ion-exchanged water), and dry it with an electric dryer at 80°C to make a pretreated SUS board. Weigh the mass of the pretreated SUS board with a balance with the last 4 digits, and take it as the initial mass (X). Mix at a ratio of 20 g of modified oil/60 mL of chloroform to prepare a modified oil/chloroform solution. Here, the modified oil was prepared by heating rapeseed oil (Fujifilm Wako Pure Chemical Industries, Ltd.) at 180° C. for 8 hours. Using a dropper, the modified oil/chloroform solution was flowed to 1 mg/cm ² at one time on an area of 25 mm×50 mm on one side of the pretreated SUS plate. The oil-adhered surface was laid flat overnight and dried to prepare a SUS board for cleaning. Weigh the mass of the SUS board for cleaning with a balance with the last 4 digits, and take it as the mass before cleaning (Y). Evaluation was performed for each cleaning composition for hard articles in the table using 3 SUS boards for cleaning. Arrange 3 SUS plates for cleaning on a balance plate BD-3 (140×140×25 mm), soak them in 40 mL of a cleaning composition for hard objects, and place them at 25°C for 20 minutes. Thereafter, it was rinsed with tap water for 1 minute at a mechanical force of 300 rpm using a Leenerts testing machine, and then left flat overnight to dry it. Weigh the mass of the cleaned SUS plate after drying with a 4-digit balance, and take it as the mass after cleaning (Z). According to the initial mass (X), the mass before cleaning (Y) and the mass after cleaning (Z), the cleaning rate is calculated according to the following formula. Cleaning rate (%) = [mass before cleaning (Y) - mass after cleaning (Z)] / [mass before cleaning (Y) - initial mass (X)] × 100

[table 5] Example 1b 2b 3b 4b 5b 6b 7b 8b 9b 10b Cleaner composition for hard objects Deployment ingredients︵mass%︶ (a _x ) AMIET 102 6 8 6 8 8 4 6 8 6 8 (b _x ) E102-KG E105 6 4 E108 6 4 E120 4 8 E121 E705 6 4 E707 6 4 AG-124 (c _x ) Emal 20C citric acid Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount water margin margin margin margin margin margin margin margin margin margin total 100 100 100 100 100 100 100 100 100 100 pH value(20℃) 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 Hydrophilic-lipophilic index of the composition 9.4 9.3 10.6 10.1 11.2 13.2 9.8 9.6 10.6 10.1 Cleaning rate of modified oil stain (%) 26.8 32.8 42.4 44.9 40.0 41.7 46.8 35.4 48.0 61.3 Exterior cloudy cloudy transparent transparent transparent transparent cloudy cloudy transparent transparent

[Table 6] Example comparative example 11b 12b 13b 14b 15b 16b 17b 18b 1b 2b 3b 4b 5b 6b 7b Cleaner composition for hard objects Deployment ingredients︵mass%︶ (a _x ) AMIET 102 6 4 3.8 3.6 3.4 10 10 10 6 8 4 2 10 2 2 (b _x ) E102-KG 6 4 8 10 2 E105 E108 E120 2 10 E121 2 10 E705 E707 2 AG-124 6 8 7.6 7.2 6.4 (c _x ) Emal 20C 0.6 1.2 2.2 citric acid Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount Adjustment amount water margin margin margin margin margin margin margin margin margin margin margin margin margin margin margin total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 pH value(20℃) 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 7.1 Hydrophilic-lipophilic index of the composition 10.3 10.7 10.8 11.0 11.2 10.13 10.36 9.6 7.76 8.21 7.31 6.87 8.65 14.27 15.39 Cleaning rate of modified oil stain (%) 48.8 57.0 57.54 66.67 67.47 56.0 50.7 24.5 6.1 6.4 3.0 2.7 13.2 19.0 14.0 Exterior cloudy transparent transparent transparent transparent transparent transparent cloudy cloudy cloudy cloudy cloudy cloudy transparent transparent

[Table 7] Example 19b 20b 21b 22b Cleaner composition for hard objects Deployment ingredients︵mass%︶ (a _x ) AMIET 102 6 6 6 6 (b _x ) AG-124 6 6 6 6 (d _x ) Amide type nonionic surfactant 2 (d' _x ) Betaine Surfactant (e _x ) Diethylene glycol butyl ether 3 8 citric acid Adjustment amount Adjustment amount Adjustment amount Adjustment amount water margin margin margin margin total 100 100 100 100 pH value(20℃) 7.1 7.1 7.1 7.1 (d)/surfactant total amount (mass %) 0.00 0.00 0.00 14 (d')/total amount of surfactant (mass%) 0.00 0.00 0.00 0.00 (e)/surfactant total amount (mass %) 25 67 0.00 0.00 (e)/(a) (mass ratio) 2.00 0.75 0.00 0.00 Hydrophilic-lipophilic index of the composition 11.3 13.3 10.3 9.6 Cleaning rate of modified oil stain (%) 49.2 31.8 48.8 27.1 Exterior cloudy transparent cloudy cloudy

Claims (23)

A cleaning composition for hard articles, which contains the following (a) component, the following (b) component, and the following (c) component, and The mass ratio of the content of (a) component to the content of (c) component (a)/(c) is 0.40 to 5.0, Optionally contain (d) one or more surfactants selected from betaine-type surfactants and amide-type nonionic surfactants [hereinafter referred to as (d) component], and the content of (d) component is relative to the composition The total amount of surfactant in it is less than 10% by mass, (a) Component: polyoxyalkylene alkyl or alkenylamine having an alkyl or alkenyl group with a carbon number of 6 to 20, and the average addition molar number of the oxyalkylene group is 1 to 5 Component (b): One or more surfactants selected from nonionic surfactants and anionic surfactants (however, component (a) and amide-type nonionic surfactants are excluded) (c) Component: solvent. The hard article cleaning agent composition as claimed in item 1, wherein the mass ratio of the content of (a) component to the content of (b) component (a)/(b) is 0.01 to 3. The cleaning composition for hard objects as claimed in claim 1 or 2, which has a pH value of 5 to 11 at 20°C. The cleaning composition for hard articles according to any one of claims 1 to 3, wherein component (c) is one or more solvents selected from glyceryl ether, glycol ether and polypropylene glycol. The cleaning composition for hard articles according to any one of Claims 1 to 4, which contains 0.01 mass % to 30 mass % of (a) component. A method for cleaning hard objects, which comprises contacting the cleaning composition for hard objects according to any one of Claims 1 to 5 with hard objects to which dirt is attached. The method for cleaning hard objects according to Claim 6, which makes the above-mentioned cleaning composition for hard objects foam and contacts the hard objects. The method for cleaning hard objects according to claim 7, which makes the above-mentioned cleaning agent composition for hard objects contact the hard objects by foaming with a sponge or a spray device equipped with a foam forming mechanism. The method for cleaning hard objects as claimed in any one of claims 6 to 8, wherein the hard objects are tableware. A cleaning composition for hard objects, which contains the following (a _x ) component and the following (b _x ) component, and the hydrophilic and lipophilic index of the entire composition is 9 to 14.2, (a _x ) component: A polyoxyalkylene alkyl or alkenylamine (b _x ) component having an alkyl or alkenyl group with a carbon number of 8 to 18 and an average addition mole number of the oxyalkylene group of 1 to 5: not Ionic surfactants (however, the ( _ax ) component and amide-type nonionic surfactants are excluded). The hard object cleaning composition as claimed in claim 10, wherein the mass ratio of the content of the component (a _x ) to the content of the component (b _x ), that is, (a _x )/(b _x ), is 0.01 to 30. According to claim 10 or 11, the cleaning composition for hard objects has a pH value of 5 to 11 at 20°C. The cleaning composition for hard articles according to any one of Claims 10 to 12, which optionally contains the following (c _x ) component, (c _x ) component: anionic surfactant. The cleaning composition for hard articles according to claim 13, wherein the content of component (c _x ) is 50% by mass or less relative to the total amount of surfactants in the composition. The cleaning composition for hard objects as any one of claims 10 to 14, which arbitrarily contains the following (d _x ) component, and the content of (d _x ) component is less than the total amount of the surfactant in the composition 10% by mass, (d _x ) component: amide type nonionic surfactant. The cleaning composition for hard objects as any one of claims 10 to 15, which arbitrarily contains the following ( _ex ) component, and the content of ( _ex ) component is less than the total amount of the surfactant in the composition 50% by mass, ( _ex ) component: a hydrophilic solvent having a hydrocarbon group having a carbon number of 9 or less and having a solubility in water of 5 g/100 g or more at 25°C. The cleaning agent composition for hard objects as any one of claims 10 to 16, wherein (b _x ) component is selected from (b _x 1) polyoxyalkylene alkyl ether, (b _x 2) alkyl ( One of poly)glycoside, (b _x 3) polyoxyalkylene fatty acid ester, (b _x 4) polyglycerol fatty acid ester, and (b _x 5) (poly)oxyalkylene sorbitan fatty acid ester The above non-ionic surfactants. The cleaning composition for hard articles as claimed in any one of claims 10 to 17, wherein the component (b _x ) is selected from one or more of alkoxylate type nonionic surfactants and alkyl glycoside type surfactants HLB is a non-ionic surfactant with an HLB of 9 or more and 17.4 or less. A method for cleaning hard objects, which comprises contacting the cleaning composition for hard objects according to any one of Claims 10 to 18 with hard objects to which dirt is attached. The method for cleaning hard objects according to claim 19, which comprises foaming the cleaning composition for hard objects and contacting the hard objects. The method for cleaning hard objects according to claim 20, which makes the above-mentioned cleaning agent composition for hard objects contact the hard objects by foaming with a sponge or a spray device equipped with a foam forming mechanism. The method for cleaning hard objects according to any one of Claims 19 to 21, wherein the hard objects are tableware. The method for cleaning hard objects as claimed in any one of claims 19 to 22, wherein the dirt is oily dirt.